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1.
Simple “click” polycondensation metallopolymers of redox‐robust bis(ethynyl)biferrocene (biFc) and di(azido) poly(ethylene glycol) (PEG400 and PEG1000) were designed for multiple functions including improvement of water solubility and biocompatibility, the introduction of mixed valency and sensing capabilities, and as nanoparticle stabilizers for catalysis.  相似文献   

2.
By means of dielectric relaxation spectroscopy (DRS) and small-angle X-ray scattering (SAXS), we have investigated hydration behavior, solvent dynamics, and static structures of aqueous solutions of poly(ethylene glycol)-conjugated distearoyl phosphatidylethanolamine (DSPE-PEG) (molecular weight of PEG: M(PEG)= 2000, 5000, and 12,000 Da). A quantitative analysis of the bulk-water relaxation amplitude revealed the effective hydration number of a DSPE-PEG molecule per ethylene oxide monomer unit to be approximately 5.0-5.5, virtually independent of M(PEG). The overall hydration number of a DSPE-PEG molecule is ca. 20% higher than that of the corresponding normal PEG (without DSPE). This is attributed to both hydration of a charged head group of phosphoric acid in DSPE and a packing effect of PEG chains into micellar structures. The pair-distance distribution functions, p(r), extracted from the GIFT analysis of SAXS intensities show that the DSPE-PEGs form spherical-like micelles in water having the maximum diameter of approximately 16, 22, and 31 nm, respectively, for M(PEG) = 2000, 5000, and 12,000 Da and nearly identical aggregation numbers of 72 (+/-10%). The DSPE-PEG micelles behave as charged colloids whose interparticle interaction potential can be approximated by the screened Coulomb potential model. The extracted pair correlation function g(r) demonstrates that both electrostatic repulsion induced by the charged head group and excluded volume effects of the fully hydrated PEG layer contribute to repulsive interactions among the PEG-lipid micelles. This should be a key factor for the function of PEG lipids as a stabilizer of liposomes.  相似文献   

3.
A synthetic oxygen (O(2)) and carbon monoxide (CO) receptor (hemoCD) composed of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinatoiron(ii) and a per-O-methylated β-cyclodextrin dimer with a pyridine linker (Py3CD) was functionalised with poly(ethylene glycol) (PEG) to elongate the circulation time of the receptor in the bloodstream. α-PEG monocarboxylic acid (HOOC(CH(2))(3)(CO)O-PEG(mw)-OCH(3); mw = 750 or 5k) or α,ω-PEG dicarboxylic acid (HOOC(CH(2))(3)(CO)O-PEG(mw)-O(CO)(CH(2))(3)COOH; mw = 10k or 20k) was reacted with the amino group of 5-(4-aminophenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin to afford a porphyrin monomer having a PEG chain or a porphyrin dimer having a PEG linker, respectively. The ferrous complexes of these PEGylated porphyrins (PEG750-, PEG5k-, PEG10k- and PEG20k-hemoCDs) bound O(2) in aqueous solution, P(1/2) values being 6.5-8.1 Torr at pH 7.0 and 25 °C. Each PEG(mw)-hemoCD was infused into the femoral vein of a Wistar male rat. After 6 h of the infusions, 67, 82, 86 and 42% of PEG750-, PEG5k-, PEG10k- and PEG20k-hemoCD were excreted in the urine. PEG750-hemoCD with a hydrodynamic diameter (D(h)) of 3.4 nm seemed to partly leak from the blood vessels (pore size: 2-6 nm) before renal filtration (pore size: 4-14 nm). PEG5k- (D(h) = 6.2 nm) and PEG10k-hemoCDs (9.0 nm) hardly passed through the blood vessels but were fully filtered by the kidney, resulting in high excretion rates. A considerable amount of PEG20k-hemoCD (D(h) = 12.0 nm) was retained in the blood even at 6 h after administration. The present study demonstrates that the behaviour of hemoCD in blood after administration can be controlled by modification of hemoCD with PEG having an appropriate molecular weight.  相似文献   

4.
We investigate the effects of controlled poly(ethylene glycol) (PEG) doping on the behavior of pyrene, rhodamine 6G (R6G), and acrylodan-labeled bovine serum albumin (BSA-Ac) sequestered within tetramethylorthosilicate (TMOS)-derived sol-gel-processed materials. To probe the dipolarity of the local environment within the composite we performed static fluorescence measurements on pyrene as the composites aged. We found that small levels of PEG loading effected significant enhancements in the local dipolarity surrounding the average pyrene molecule. Time-resolved fluorescence anisotropy measurements were used to follow the rotational reorientation dynamics of R6G as the composites aged. As the PEG loading increased, the R6G reorientational mobility increased. Nitrogen adsorption techniques were used to quantify the effects of PEG doping level on the surface area and final xerogel pore features. A large reduction in surface area was observed with PEG doping, but no detectable change in pore size was noted. The effects of PEG doping on a biomolecule were probed by following the time-resolved fluorescence anisotropy decay of BSA-Ac. These results showed that PEG doping resulted in increased biomolecule dynamics relative to that found for a neat, undoped TMOS-derived composites. Together these results show that PEG doping can be used to tune the sol-gel-processed composite dipolarity, alter the mobility of dopants sequestered within the composite, control analyte acessibility to the sensing chemistry, and modulate the internal dynamics within a biodopant.  相似文献   

5.
Blends of poly (3-hydroxybutyrate) (PHB) with poly (ethylene glycol) (PEG), (PHB/PEG), in different proportions of 100/0, 98/2, 95/5, 90/10, 80/20 and 60/40 wt%, respectively, were investigated for their thermal properties (using differential scanning calorimetry and thermogravimetric analysis), tensile properties, water vapor transmission rate, enzymatic biodegradation (using light microscopy) and mass retention. The addition of plasticizer did not alter the thermal stability of the blends, although an increase in the PEG content reduced the tensile strength and increased the elongation at break of pure PHB.  相似文献   

6.
We report the synthesis, characterization, and photophysical properties of a new class of luminescent cyclometalated iridium(III) polypyridine poly(ethylene glycol) (PEG) complexes [Ir(N^C)2(N^N)](PF6) (HN^C=Hppy (2‐phenylpyridine), N^N=bpy? CONH? PEG1 (bpy=2,2′‐bipyridine; 1 a ), bpy? CONH? PEG3 ( 1 b ); HN^C=Hpq (2‐phenylquinoline), N^N=bpy? CONH? PEG1 ( 2 a ), bpy? CONH? PEG3 ( 2 b ); HN^C=Hpba (4‐(2‐pyridyl)benzaldehyde), N^N=bpy? CONH? PEG1 ( 3 )) and their PEG‐free counterparts (N^N=bpy? CONH? Et, HN^C=Hppy ( 1 c ); HN^C=Hpq ( 2 c )). The cytotoxicity and cellular uptake of these complexes have been investigated by the MTT assay, ICPMS, laser‐scanning confocal microscopy, and flow cytometry. The results showed that the complexes supported by the water‐soluble PEG can act as biological probes and labels with considerably reduced cytotoxicity. Because the aldehyde groups of complex 3 are reactive toward primary amines, the complex has been utilized as the first luminescent PEGylation reagent. Bovine serum albumin (BSA) and poly(ethyleneimine) (PEI) have been PEGylated with this complex, and the resulting conjugates have been isolated, purified, and their photophysical properties studied. The DNA‐binding and gene‐delivery properties of the luminescent PEI conjugate 3 ‐PEI have also been investigated.  相似文献   

7.
《先进技术聚合物》2018,29(9):2467-2476
Poly (caprolactone) membranes with addition of different poly (ethylene glycol) concentrations were prepared for separation of water/isopropanol azeotropic mixture by pervaporation process. Different characterization tests including Fourier transform infrared, scanning electron microscopy, water contact angle, and thermogravimetric analysis were carried out on the prepared membranes. In addition, the effect of poly (ethylene glycol) PEG content on the swelling degree and the performance of the prepared membranes in pervaporation process were investigated. According to the obtained results, all the membranes were water selective and the blend membrane containing 3 wt% PEG exhibited the best pervaporation performance with a water flux of 0.517 kg/m2 hour and separation factor of 1642 at the ambient temperature. Hydrophilicity improvement of the blend membranes was confirmed by constant decrease in water contact angle of the membranes as PEG content increased in the casting solution. Scanning electron microscopy cross‐sectional images indicated that the blend membranes containing PEG had a closed cellular structure. Furthermore, mechanical and thermal properties of the membranes decreased by adding PEG.  相似文献   

8.
A series of supramolecular inclusion complex (IC) films were formed by threading α‐cyclodextrin (α‐CD) molecules over poly(ethylene glycol) (PEG), according to the designed ratio of α‐CD/PEG. Because of containing α‐CD‐PEG inclusion crystallites as physical crosslinks and uncovered PEG crystallites as “switch phase”, the resulting supramolecular α‐CD‐PEG partial ICs displayed a shape memory effect. The properties of the materials were investigated by 1H‐NMR, X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and swelling measurement. It was found that the casting temperature, solvent, and the ratio of α‐CD‐PEG inclusion/PEG had great influence on the formation and properties of α‐CD‐PEG partial ICs. The modes of complexes on different conditions were proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 951–957, 2010  相似文献   

9.
Polyoxymethylene (POM)/multiwalled carbon nanotubes (MWNTs) nanocomposites were prepared through a simple solution‐evaporation method assisted by ultrasonic irradiation. To enhance the dispersion of MWNTs in POM, MWNTs were chemically functionalized with PEG‐substituted amine (MWNT‐g‐PEG), which exhibited strong affinity with POM due to their similar molecular structure. The thermal conductivity and the mechanical properties of the composites were investigated, which showed that the thermal conductive properties of POM were improved remarkably in the presence of MWNTs, whereas reduced by using MWNT‐g‐PEG due to the heat transport barrier of the grafted‐PEG‐substituted amine chain. A nonlinear increase of the thermal conductivity was observed with increasing MWNTs content, and the Maxwell‐Eucken model and the Agari model were used for theoretical evaluation. The relatively high effective length factor of the composite predicted with mixture equation indicated that there were few entangles of MWNTs for the samples of MWNT‐g‐PEG in the composites. The mechanical strength of the composites can be improved remarkably by using suitable content of such functionalized MWNTs, and with the increase of the aliphatic chain length of PEG‐substituted amine, the toughness of the composites can be enhanced. Transmission electron microscope result indicated that MWNT‐g‐PEG exhibited strong affinity with POM and a good dispersion of MWNTs was achieved in POM matrix. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 905–912, 2010  相似文献   

10.
温敏性PCL-PEG-PCL水凝胶的合成、表征及蛋白药物释放   总被引:2,自引:0,他引:2  
考察了温敏性PCL-PEG-PCL水凝胶中聚乙二醇(PEG)及聚己内酯(PCL)不同嵌段组成对其溶胶-凝胶相转变温度以及亲水性药物(牛血清白蛋白, BSA)释放速率的影响. 采用开环聚合法, 以辛酸亚锡为催化剂、PEG1500/PEG1000为引发剂, 与己内酯单体发生开环共聚, 合成了一系列具有不同PEG和PCL嵌段长度的PCL-PEG-PCL型三嵌段共聚物. 通过核磁共振氢谱及凝胶渗透色谱对其组成、结构及分子量进行了表征. 共聚物的溶胶-凝胶相变温度由翻转试管法测定. 利用透射电镜、核磁共振氢谱及荧光探针技术证实了该材料在水溶液中胶束的形成. 以BSA为模型蛋白药物, 制备载药水凝胶, 利用microBCA法测定药物在释放介质中的浓度, 研究其体外释放行为. 实验结果表明, 共聚物的溶胶-凝胶相变温度与PCL及PEG嵌段长度紧密相关, 即在给定共聚物浓度情况下, 固定PEG嵌段长度而增加PCL嵌段长度, 会导致相变温度降低; 而固定PCL嵌段长度而增加PEG嵌段长度, 其相变温度相应升高. 水凝胶中蛋白药物的释放速率与疏水的PCL嵌段长度无关, 而与亲水的PEG嵌段长度密切相关, 即PEG嵌段越长, 蛋白药物释放越快.  相似文献   

11.
Poly(lactic acid) (PLA)/PEG/nano-silica composite degradable films have been prepared by solvent casting method. IR measurements showed that vibration of C–O–C group was confined by silica network. SEM results showed that nano-silica particles were dispersed uniformly in the PLA/PEG matrix. TGA results indicated that the thermal decomposition temperature rose with the increase of nano-silica content. The tensile strength of composite film increased by the addition of nano-silica particles into PLA/PEG matrix. The degradation rate of PLA/PEG/nano-silica composites increased with the acidic medium of degradation. On the other hand, the slower degradation was obtained in the neutral buffer solution. PLA/PEG/nano-silica composites were found to exhibit almost similar degradation behavior as that of PLA/PEG films.  相似文献   

12.
A simple but efficient strategy has been developed for the synthesis of novel di‐, tri‐, multi‐, and star‐block copolymers comprising poly(ethylene glycol) (PEG) and polyisobutylene (PIB) blocks. The synthesis principle involves the coupling of appropriately terminally functionalized PEG and PIB sequences, specifically the hydrosilation of mono‐, di‐, and tetra‐allyl‐telechelic PEGs (PEG‐allyl, allyl‐PEG‐allyl, and C(‐PEG‐allyl)4 by mono‐ and di‐Si(CH3)2H telechelic PIBs (PIB‐SiH and HiS‐PIB‐SiH). Representative block copolymers, for example, PEG‐PIB, PIB‐PEG‐PIB, (‐PIB‐PEG‐)n, and C(‐PEG‐PIB)4 have been assembled and their structures determined by 1H and 13C NMR spectroscopy. The bulk and surface morphology of select triblocks have been investigated by DSC and AFM and the findings interpreted in terms of phase‐separated PEG and PIB microdomains. The swelling behavior in water of various block copolymers also has been studied. Block copolymers containing 50–70 wt % PIB produce hydrogels, the integrity of which is maintained by physical crosslinks by PIB segments. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3200–3209, 2000  相似文献   

13.
A new type of nanocapsules with an oil core, coated by poly(ethylene glycol) (PEG) was designed. The loading efficiency and the biocompatibility of the polymeric nanocapsules were evaluated when it was used as a carrier for hydrophobic agent paclitaxel. The nanocapsules were synthesized through miniemulsion polymerization of butylcyanoacrylate (BCA) with PEG as initiator. The particle size and zeta potential of nanocapsules were influenced by the PEG content in the polymerization system. Fourier transform infrared (FTIR) spectra and 1H NMR demonstrated the chemical coupling between PEG and poly(butylcyanoacrylate) (PBCA). Thermal characteristics of the copolymer were investigated by differential scanning calorimetry (DSC). The encapsulation efficiency increased concurrently with the increase of the PEG content in the system. The hemolytic assay and the cytotoxicity measurement showed that the PEG coating could significantly reduce the hemolytic potential and cytotoxicity of the nanocapsules. The results showed that the PEG-PBCA nanocapsules could be an effective carrier for hydrophobic agents.  相似文献   

14.
A series of poly(D,L-lactic-co-glycolic acid) (PLGA)/poly(ethyleneglycol) (PEG) di-block copolymers were synthesized by ring-opening polymerization of D,L-lactide and glycolide with different molecular weights of monomethoxy polyethyleneglycol (mPEG) 750, 2000 and 5000 as an initiator. The bulk properties of these co-polymers were characterized by using 1H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry (DSC). Electron spectroscopy for chemical analysis (ESCA) results, in which the blend films with the di-block copolymers showed increasing surface oxygen atomic percentage with increasing PEG chain length, indicate that PEG chain segment in the di-block copolymers is surface oriented and enriched onto the surface of the blend films. The extent of protein adsorption onto the surface of these blend films was studied, using iodine radio-labeled human serum albumin, gamma globulin and human growth hormone. The protein adsorption amount was reduced for the blend films prepared with PLGA/PEG 750 and 2000 di-block copolymers, but increased to a great extent for PLGA/PEG 5000 di-block copolymer. This is due to the increased water uptake capacity of the blend film, which absorbed more protein molecules into a swollen polymer matrix in addition to surface adsorption.  相似文献   

15.
Core‐shell structured nanoparticles of poly(ethylene glycol) (PEG)/polypeptide/poly(D ,L ‐lactide) (PLA) copolymers were prepared and their properties were investigated. The copolymers had a poly(L ‐serine) or poly(L ‐phenylalanine) block as a linker between a hydrophilic PEG and a hydrophobic PLA unit. They formed core‐shell structured nanoparticles, where the polypeptide block resided at the interface between a hydrophilic PEG shell and a hydrophobic PLA core. In the synthesis, poly(ethylene glycol)‐b‐poly(L ‐serine) (PEG‐PSER) was prepared by ring opening polymerization of N‐carboxyanhydride of O‐(tert‐butyl)‐L ‐serine and subsequent removal of tert‐butyl groups. Poly(ethylene glycol)‐b‐poly(L ‐phenylalanine) (PEG‐PPA) was obtained by ring opening polymerization of N‐carboxyanhydride of L ‐phenylalanine. Methoxy‐poly(ethylene glycol)‐amine with a MW of 5000 was used as an initiator for both polymerizations. The polymerization of D ,L ‐lactide by initiation with PEG‐PSER and PEG‐PPA produced a comb‐like copolymer, poly(ethylene glycol)‐b‐[poly(L ‐serine)‐g‐poly(D ,L ‐lactide)] (PEG‐PSER‐PLA) and a linear copolymer, poly(ethylene glycol)‐b‐poly(L ‐phenylalanine)‐b‐poly(D ,L ‐lactide) (PEG‐PPA‐PLA), respectively. The nanoparticles obtained from PEG‐PPA‐PLA showed a negative zeta potential value of ?16.6 mV, while those of PEG‐PSER‐PLA exhibited a positive value of about 19.3 mV. In pH 7.0 phosphate buffer solution at 36 °C, the nanoparticles of PEG/polypeptide/PLA copolymers showed much better stability than those of a linear PEG‐PLA copolymer having a comparable molecular weight. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

16.
The micellization of F127 (E(98)P(67)E(98)) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (r(h,app)) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G(max)(')) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.  相似文献   

17.
Biodegradable and nontoxic alternating multiblock copolymers based on poly (p-dioxanone) (PPDO) and poly (ethylene glycol) (PEG) were synthesized by the coupling reaction of two bifunctional prepolymers, a dihydroxyl-terminated PPDO and dicarboxylated PEG. The prepolymers and the resulting PPDO/PEG multiblock copolymers were characterized by various analytical techniques such as FT-IR, 1H NMR, GPC, DSC and TG. At high concentration levels above critical gelation concentration (CGC), the aqueous solution of copolymers formed a gel. Temperature-sensitive gel to sol transition behaviors were investigated by the test tube inverting method. Dynamic light scattering (DLS) was used to investigate the micelle of copolymers, whose association probably caused the gelation of the system. Therefore, this novel copolymer has a great potential in injectable drug-delivery system for long-term delivery of drugs.  相似文献   

18.
Polymer coatings with features of differing hydrophilicity, mobility, and topography, distributed across a substrate in microscopic and nanoscopic patches were designed as complex materials equipped with sufficient variability in composition, structure, and dynamics to inhibit interactions associated with biomacromolecular fouling. These complex polymer coatings were prepared by the in situ phase separation and crosslinking of mixtures of hyperbranched fluoropolymer (HBFP) and diamino‐terminated poly(ethylene glycol) (PEG), for which the degree of crosslinking, compositions, topographies, and morphologies were varied by alteration of the PEG/HBFP stoichiometries (14, 29, 45, and 55 wt % PEG). This article examines the physicochemical details of HBFP–PEG network coatings prepared on glass substrates, functionalized by 3‐aminopropyltriethoxysilane, as characterized by atomic force microscopy (AFM), contact‐angle measurements, X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetric analysis. Upon incubation in water or artificial seawater, the surfaces underwent reconstruction, which was believed to be driven by the swelling of the PEG domains and the energetic favorability offered by the segregation of PEG to the solid–water interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6193–6208, 2004  相似文献   

19.
Two α-septithiophenes substituted at the third position of the middle ring with polyethyleneglycol of different molecular weights (PEG 1000 and PEG 2000) were synthesized using Suzuki condensation. Their structural characterization was performed by 1H NMR and FT-IR. The thermal behavior of the new synthesized oligothiophenes was investigated by differential scanning calorimetry (DSC) and thermogravimetrical (TGA) analysis. Photophysical properties in solutions were evaluated by UV-vis and fluorescence measurements using different solvents. The amphiphilic nature of the synthesized oligothiophenes and the presence of the PEG side chains induced self-dispersibility in water and the possibility of fluorescent nanoparticles forming by self-assembling. The size of nanoparticles in water was assessed by DLS and AFM investigations.  相似文献   

20.
The poly(ethylene glycol)/poly(2‐(N,N‐dimethylamino)ethyl methacrylate) (PEG/PDMAEMA) double hydrophilic block copolymers were synthesized by atom transfer radical polymerization using mPEG‐Br or Br‐PEG‐Br as macroinitiators. The narrow molecular weight distribution of PEG/PDMAEMA block copolymers was identified by gel permeation chromatography results. The thermosensitivity of PEG/PDMAEMA block copolymers in aqueous solution was revealed to depend significantly on pH, ionic strength, chain structure, and concentration of the block copolymers. By optimizing these factors, the cloud point temperature of PEG/PDMAEMA block copolymers can be limited within body temperature range (30–37 °C), which suggests that PEG/PDMAEMA block copolymers could be a good candidate for drug delivery systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 503–508, 2010  相似文献   

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